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The present invention relates generally to the field of photovoltaic device manufacture and in particular, the invention provides a self aligning method of metallization formation in a photovoltaic device.
Many approaches exist for diffusing dopants of one polarity into the surface of a substrate doped with the opposite polarity so as to form a p-n junction. One such approach involves the deposition of a dielectric containing the appropriate dopants onto the surface of the oppositely doped substrate followed by appropriate thermal treatment to allow the dopants from within the dielectric to diffuse into the substrate surface. Examples of techniques for carrying out the thermal treatment include conventional quartz tube furnaces infrared belt furnaces rapid thermal anneals, and the use of lasers.
It is also well documented in the literature, that spatially selective emitters can be important for the achievement of high efficiencies. Heavy doping beneath the metal contact is important, both for reducing contact resistance and also to minimise the contribution made to the dark saturation current for the solar cell by the silicon/metal interface region. For the latter, the heavy doping makes it possible to locate the high surface recombination velocity region associated with the metal/silicon interface more than a minority carrier diffusion length away from the p-n junction, thereby minimising the contribution made to the device dark saturation current by the metal contact. The highest performance commercially available solar cells achieve the heavy doping under the metal by forming a groove through a lightly diffused emitter at the top surface and then subsequently diffusing large amounts of dopant into the walls of the exposed grooves prior to plating the metal contacts also within the grooves where the heavy doping exists. This provides the advantages described above while leaving the majority of the top surface lightly diffused, therefore preventing the formation of a surface dead layer which would otherwise exist if the heavy doping extended across the light receiving surface. The lightly diffused emitter in conjunction with adequate surface passivation enables the achievement of high carrier collection probabilities for carriers generated throughout the depth of the lightly diffused emitter. The disadvantages of this approach include the necessity for two independent diffusion processes, which adds cost and complexity and also possible degradation of the substrate quality through the long high temperature exposure needed to achieve the heavy doping within the grooved region. A third disadvantage of this approach results from the necessity for a damage/debris removal etch following the grooving process to prepare the silicon surfaces within the groove for the subsequent diffusion.
Another approach for achieving the selective emitter with heavy doping beneath the metal contact has been reported by U.Besi-Vetrella et alia (“Large area. Screen Printed Silicon Solar Cells with selective Emitter made by Laser Overdoping and RTA Spin-on Glasses”. 26
The present invention provides a self aligning method of forming contact metallization in a solar cell, the method including the steps of:
a) on a surface of a semiconductor substrate of a first dopant type, forming a continuous layer of dopant source material of a second dopant type of opposite dopant polarity to that of the first dopant type, the source material being selected to also act or to be made able to act as a surface passivation layer and a metallization pattern mask;
b) thermally treating the dopant source and the semiconductor surface carrying the dopant source, whereby a surface region of the second dopant type is formed in the semiconductor material, the first and second doped semiconductor types forming a p-n junction beneath the surface of the semiconductor substrate;
c) locally heating the dopant source and the underlying semiconductor surface to cause melting of the surface region in zones where metallization is required to contact to the surface region whereby the melted zones of the semiconductor surface region are more heavily doped from the dopant source and the overlying dopant source material is disrupted to expose the more heavily doped surface zones;
d) forming metallization over the heavily doped surface zones such that connection to the surface region of the semiconductor material is made through the disruption in the dopant source layer to the heavily doped surface zones.
Preferably, the source material will also be chosen to form an antireflection coating.
In one embodiment, the dopant source layer is a single layer of dielectric material carrying a dopant source whereby the dielectric material acts as a dopant source, a passivation layer, a metallization mask and perhaps also an anti reflection coating, however, in other embodiments, a doped passivation layer is provided with a dielectric layer formed over it to act as a metallization mask, in which case, the localised heating step must disrupt both the dopant passivation layer and the dielectric layer. In this case, one of the layers may also act as an antireflection layer or a separate antireflection layer may be provided.
The first heating step is performed with parameters chosen to result in a surface region doping level in the range of 50-800 ohms per square and preferably in the range of 80-200 ohms per square.
The second localised heating step is preferably performed with a laser to enable concentrated heating in a small well defined area of the device. The laser may be a continuous wave laser or a pulsed (Q-switched) laser, however, in the latter case, the laser will generally be defocussed to prevent (or at least minimise) ablation during the heating step or else a wavelength at which laser energy will be absorbed close to the surface of the substrate.
Embodiments of the invention will now be described by way of example, with reference to the accompanying drawings in which:
Referring to
A laser
Excessive laser power will lead to the ablation of excessive amounts of heavily doped silicon and possibly even the overlying dielectric material. This can lead to insufficient dopant remaining in the grooved walls for good device performance. At the other extreme, insufficient laser power can lead to the inability to plate the heavily doped regions which remain protected by the overlying dielectric or alternatively insufficient dopants even penetrating into the silicon to facilitate good device performance. Between these extremes, there are wide ranges of laser conditions that can be used to satisfy the requirements of this invention. For example, a neodymium YAG laser with sufficient power can be used on continuous-wave mode to form the heavily doped region shown in
Following the laser treatment, the surface of the device can be directly plated provided the electroless plating solution used can tolerate thin surface oxides formed naturally during the laser treatment. If a plating solution is used that cannot tolerate surface native oxides, then a diluted hydrofluoric acid solution can be used for a short period to remove the thin surface oxides without significant damage to the remaining dielectric that protects the lightly diffused emitter regions. Common electroless plating approaches include an initial thin layer of nickel which following sintering at typically 350-400° C. is plated by electroless copper to the desired height following which a brief submersion in an “immersion silver” solution can be used to provide a thin silver capping layer over the copper to prevent future oxidation, possible interaction with encapsulants and make the metal contact more easily soldered.
The procedures described above can be interrupted through the inclusion of additional processes for other purposes such as the formation of the rear metal contact. For example, the rear metal contact may be formed on the rear surface
Embodiments of the present invention are applicable to both planar and rough surfaces such as those textured or machined, although the laser parameters may need slight adjustment when swapping between the two surface types. For example, if the laser operating parameters are adjusted for good results with a planar surface when using a defocussed beam, the power should be slightly reduced for comparable results with a textured surface due to the more effective coupling of the laser energy into the textured silicon surface. The textured surfaces will also obliquely couple some of the laser light into the silicon with the net result that the laser processed n
The following two fabrication processes are typical examples of how the above invention can be incorporated into a solar cell.
1.1 Saw damage removal etch and anisotropic texturing in dilute sodium hydroxide at approximately 90° C.;
1.2 Application of phosphorus spin-on diffusion source plus drying;
1.3 Rapid thermal annealing of wafer top surface to form lightly diffused emitter preferably in the range 80-200 ohms per square;
1.4 Application of the rear metal contact such as by vacuum evaporation or screen-printing of aluminium or silver with small aluminium concentration; drying if appropriate:
1.5 Rear metal sintering such as at 820° C. in oxygen/nitrogen ambient for a screen printed contact so as to simultaneously fire the metal paste while oxidising the top surface dielectric to increase its resistance to the metal plating solutions;
1.6 Laser processing to pattern the dielectric layer while simultaneously melting the underlying silicon so as to form the n
1.7 Brief dilute hydrofluoric acid treatment to prepare metal plating surface, Electroless nickel plating at approximately 90° C. for 5 minutes;
1.8 Sintering of nickel in the range of 350° C.-450° C. in inert atmosphere such as nitrogen, argon or forming gas;
1.9 Further two minutes of nickel plating prior to lengthy electroless copper plating at approximately 50° C. until the desired thickness of copper is achieved;
1.10 “Flash” immersion silver deposition onto the copper surface;
1.11 Edged junction isolation such as by laser grooving, edge cleavage or plasma etching or no edge isolation at all if not necessary.
In some implementations of the above processes, an additional oxide removal step from the surface of the rear metal prior to plating may be necessary depending on the type of metal used and the oxidation conditions during sintering. For instance, screen-printed aluminium after firing in an oxygen ambient forms a very thick oxidised layer which requires special treatment for removal as well documented in the literature.
2.1 Saw damage removal etch and an isotropic texturing in dilute sodium hydroxide at approximately 90° C.;
2 1 Diffusion source deposition as a surface dielectric;
2.3 Formation of the lightly diffused emitter by heating at approximately 800° C. for 20 minutes depending on the dielectric type used;
2.4 Coin stacking of wafers for edge junction isolation via plasma etching;
2.5 Deposition of a second dielectric layer on top of the diffusion source to provide subsequent masking for the electroless plating solutions and an antireflection coating. Examples of such a dielectric would be atmospheric CVD of titanium dioxide or else low pressure CVD of silicon nitride or alternatively the first dielectric deposition prior to the formation of the lightly diffused emitter could have for instance, also been silicon nitride but already containing phosphorus dopants so as to avoid the deposition of two separate dielectric layers;
2.6 Screen print rear metal contact such as with aluminium doped silver paste, and dry;
2.7 Fire rear metal contact such as in an infrared belt furnace at 780° C. for approximately two minutes;
2.8 Carry out laser processing equivalently to step 1.6 in example 1;
2.9 Electroless plating of front and rear metal contacts as per steps 1.8 to 1.10 from example 1;
Many variations to the individual processes above could be used such as applying the metal contact prior to light emitter formation so as both processes can be simultaneously carried out with a single thermal process. Another example would be the inclusion of an oxidation process as part of step 2.3 to convert the existing dielectric into one that is able to act as a plating mask. This would potentially alleviate the need for the second dielectric in step 2.5.
Resulting device performance falls slightly behind that of the buried contact solar cell when the metallization pattern is optimised for maximum performance. The slightly higher losses result primarily from increased resistive losses that result from the poorer aspect ratio for the metallization. However, for most commercial solar cells, interconnect wires are used across the entire length of the cell therefore minimising the length of metal fingers needed to carry current from the edges of the cell across to the interconnects. This approach minimises the advantage of the buried contact solar cell with the present invention being able to achieve virtually the same performance on float zone material. On thermally sensitive material which includes many types of commercial grade substrates, this invention has advantages over the conventional buried contact solar cell by minimising the wafer's exposure to high temperatures and also reducing the length of time needed for the thermal processes. Higher performance may therefore be expected from this invention for some commercial substrates compared to the buried contact solar cell.
In the examples given above, the invention has been applied to the light receiving surface
3.1 Saw damage removal etch and anisotropic texturing in dilute sodium hydroxide at approximately 90° C.;
3.2 Application of dielectric containing n-type dopants onto the top surface;
3.3 Application of dielectric containing p type dopants onto the rear surface;
3.4 Thermal treatment to lightly diffuse n-type emitter and a p-type back-surface field across the rear. If necessary the thermal process includes treating the dielectric such as through oxidation to giver adequate resistance to the plating solutions;
3.5 Laser processing and patterning of the front dielectric;
3.6 Laser processing of the rear dielectric;
3.7 Simultaneous electroless metal plating of front and rear metal contact.
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.